CN101821819B - Transparent conducive film and method for producing the same - Google Patents

Transparent conducive film and method for producing the same Download PDF

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Publication number
CN101821819B
CN101821819B CN2008801121097A CN200880112109A CN101821819B CN 101821819 B CN101821819 B CN 101821819B CN 2008801121097 A CN2008801121097 A CN 2008801121097A CN 200880112109 A CN200880112109 A CN 200880112109A CN 101821819 B CN101821819 B CN 101821819B
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nesa coating
film
target
magnesium
carbon
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CN101821819A (en
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久慈俊郎
千叶雅史
本城贵充
小户田小一郎
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Kuji Toshiro
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0635—Carbides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5846—Reactive treatment

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Manufacturing Of Electric Cables (AREA)
  • Non-Insulated Conductors (AREA)
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Abstract

Disclosed is a transparent conductive film containing oxygen, hydrogen and at least one element (A) selected from the group consisting of magnesium, carbon, silicon and boron. This transparent conductive film can be produced, for example, by forming a film containing magnesium and the element (A) on a substrate by using a target containing magnesium and a target containing at least one element (A) selected from the group consisting of carbon, silicon and boron, and then maintaining the thus-formed film in an atmosphere containing water.

Description

Nesa coating and method of manufacture thereof
Technical field
The present invention relates to nesa coating and method of manufacture thereof, at length say, the present invention relates to not use the nesa coating and the method for manufacture thereof of the indium that adopts in the existing main flow nesa coating.
Background technology
Nesa coating is the film that has visible light transmission and electroconductibility concurrently.
The resistivity of nesa coating is low and visible light is high-transmission rate, so to be widely used as with the liquid-crystal display be the transparency electrode of flat-panel monitor or solar cell etc. at center.In addition, the transparent and electrically conductive film that gets at the surface of resin film substrate this nesa coating of formation for example is used as the electrode of transparent touch-sensitive panel or EL (electroluminescent) flat lamp.
As nesa coating, multiple material is studied, but most of nesa coating of practicability is to be ITO (tin indium oxide) film of principal constituent with Indium sesquioxide and White tin oxide now.
But along with the increase as the landings of the flat-panel monitor of main application etc., the demand of ito thin film is also enlarging in recent years; In addition; As raw-material indium is rare metal (Clarke number 0.00001), so price is surging, the resource exhaustion problem is serious day by day.
So, the attention rate of the nesa coating (ITO equivalent material) that do not use indium is improved.As representational ITO equivalent material; The nesa coating of known zinc oxide (ZnO) class; The research of existing nesa coating as the ITO equivalent material is principal constituent with ZnO nearly all, suitably uses other composition as minor component (for example with reference to patent documentation 1).
Above-mentioned Zinc-oxide-based nesa coating is compared with the situation of using Indium sesquioxide, and the prices of raw and semifnished materials are cheap, help industrial production, but Zinc-oxide-based nesa coating is slightly poorer than above-mentioned ito thin film aspect electroconductibility.In addition, there is following problems in Zinc-oxide-based film: when film forms because of crystalline defective etc. causes resistivity unstable, or to the weather resistance of humidification, heating, acid or alkali also than ito thin film difference.And the Clarke number of zinc also has only 0.004, is rare metal.
As stated, have superiority though Zinc-oxide-based film is compared aspect cost with ito thin film, still used rare metal, this external electroconductibility and weather resistance aspect also still have room for improvement.
Patent documentation 1: Japanese Patent Laid is opened the 2006-200016 communique
The announcement of invention
As stated, the attention rate to the ITO equivalent material improves.As the ITO equivalent material, reported the nesa coating of multiple ZnO class, but still had room for improvement as the ITO equivalent material.
So, the object of the present invention is to provide a kind of neither ito thin film, neither the ZnO class the new nesa coating and the method for manufacture thereof of nesa coating.
The inventor has carried out conscientiously research to the problems referred to above, has found a kind of new nesa coating and method of manufacture thereof, thereby has accomplished the present invention.
That is, nesa coating of the present invention comprises: magnesium is selected from least a kind of element (A) of carbon, silicon and boron, oxygen, hydrogen.
As nesa coating of the present invention, preferably comprise the nesa coating of magnesium, carbon, oxygen, hydrogen.Magnesium that this nesa coating comprised and the atomic ratio of carbon (magnesium/carbon) are preferably 0.3～20.
The crystalline structure that better is nesa coating has the brucite structure.
Nesa coating of the present invention can obtain through following method: use magniferous target of bag and the target that comprises at least a kind of element (A) that is selected from carbon, silicon and boron, on substrate, form the film that comprises magnesium and this element (A), this film is remained in the moisture atmosphere.
Better be to obtain nesa coating of the present invention: use magniferous target of bag and the carbonaceous target of bag, on substrate, form the film that comprises magnesium and carbon, this film is remained in the moisture atmosphere through following method.
Better be that said moisture atmosphere is to comprise in the atmosphere of water vapour or in the water.
Better be that said film forming is carried out through the cosputtering method.
The method of manufacture of nesa coating of the present invention is characterised in that, uses magniferous target of bag and the target that comprises at least a kind of element (A) that is selected from carbon, silicon and boron, on substrate, forms the film that comprises magnesium and this element (A), and this film is remained in the moisture atmosphere.
The method of manufacture of nesa coating of the present invention is characterised in that, uses magniferous target of bag and the carbonaceous target of bag, on substrate, forms the film that comprises magnesium and carbon, and this film is remained in the moisture atmosphere.
In addition; Nesa coating of the present invention can obtain through following method: use magniferous evaporation source of bag and the evaporation source that comprises at least a kind of element (A) that is selected from carbon, silicon and boron; On substrate, form the film that comprises magnesium and this element (A), this film is remained in the moisture atmosphere.
In addition; The method of manufacture of nesa coating of the present invention is characterised in that; Use magniferous evaporation source of bag and the evaporation source that comprises at least a kind of element (A) that is selected from carbon, silicon and boron, on substrate, form the film that comprises magnesium and this element (A), this film is remained in the moisture atmosphere.
The visible light transmission of nesa coating of the present invention and electroconductibility are all good.In addition, the Clarke number of the magnesium that nesa coating of the present invention comprised is 1.98, does not have the problem of resource exhaustion.
The simple declaration of accompanying drawing
Fig. 1 be expression when remaining in the MgC film that obtains among the embodiment 1 in the atmosphere through the time figure that changes.(a-1) just after the film forming, (a-2) film forming after 5 minutes, (a-3) film forming after 10 minutes, (a-4) film forming are after 15 minutes.
Fig. 2 is the figure of the transmittance of the nesa coating that obtains among the embodiment 1 of expression.
Fig. 3 is the X-ray diffraction result of the nesa coating that obtains among the embodiment 1.
Fig. 4 is the figure of the composition of the nesa coating that obtains among the embodiment 1 of expression.The atom % of the longitudinal axis representes atomic ratio (Atomic%).
Fig. 5 is the figure of the smoothness (arithmetic average roughness (Ra) 43nm) of the nesa coating that obtains among the embodiment 1 of expression.
Fig. 6 is the figure of the surface shape of the nesa coating that obtains among the embodiment 1 of expression.
Fig. 7 is the figure of the ratio resistance value of the nesa coating that obtains among the embodiment 1 of expression.
The best mode that carries out an invention
Below, specify the present invention.
[nesa coating]
Nesa coating of the present invention comprises: magnesium is selected from least a kind of element (A) of carbon, silicon and boron, oxygen, hydrogen.
As said element (A), consider from the angle of the electroconductibility of nesa coating, better be to comprise carbon at least.
In addition, the atomic ratio of magnesium in the nesa coating of the present invention and said element (A) (magnesium/element (A)) better is in 0.5～10 scope normally in 0.3～20 scope, is more preferably in 1～5 scope.If said atomic ratio is in said scope, then the light transmission of nesa coating and electroconductibility improve.
When said element (A) was carbon, the atomic ratio of magnesium and carbon (magnesium/carbon) better was in 0.5～10 scope normally in 0.3～20 scope, is more preferably in 1～5 scope.If said atomic ratio is in said scope, then the light transmission of nesa coating and electroconductibility improve.
In addition, the atomic ratio of magnesium and oxygen (magnesium/oxygen) in 0.48～0.53 scope, better is in 0.49～0.52 scope usually.
In addition, the atomic ratio of oxygen and hydrogen (oxygen/hydrogen) in 0.5～1.5 scope, better is in 0.9～1.1 scope usually.
Only otherwise can cause detrimentally affect to light transmission and electroconductibility, nesa coating of the present invention also can comprise other element.As other element, the for example nitrogen of can giving an example.
< structure of nesa coating >
Better be in the nesa coating of the present invention, magnesium, said element (A), oxygen and hydrogen distribute in whole this nesa coating equably.If as above-mentioned, distribute equably, then the deviation of characteristics such as the light transmission of whole nesa coating and electroconductibility reduces.
Above-mentioned " distributing equably " is meant that each composition segregation-free ground distributes.
The thickness of nesa coating of the present invention in the scope of 0.1～5.0 μ m, better is in the scope of 1.0～3.5 μ m usually.If thickness in said scope, then can obtain to have the nesa coating of high light transmittance and electroconductibility.Said thickness is 2 the average film thickness that records with AFM (AFM) and SEM (scanning electron microscope).
About the crystalline structure of nesa coating of the present invention, consider that from the angle of visible light transmission and electroconductibility the crystalline structure of this nesa coating preferably possesses Mg (OH) 2Symmetric structure, i.e. brucite structure.Said structure can be confirmed through the angle of diffraction of Analysis of X ray diffraction peaks.Known in the past nesa coating all is an oxide compound, but is the structure of the nesa coating of brucite structure according to above-mentioned crystalline structure, can confirm the oxide-based nesa coating of these nesa coating right and wrong.
In addition, though element (A) with which kind of state exists described in the crystalline structure of unclear nesa coating of the present invention, with Mg (OH) 2The X-ray diffraction peak of X-ray diffraction peak and nesa coating of the present invention find (001) peak of nesa coating of the present invention and Mg (OH) when comparing 2(001) peak compare to the low angle side shifting, promptly the interfloor distance of brucite structure enlarges, so the inventor infers that said element (A) is present in the interlayer of brucite structure.Because the crystalline structure of nesa coating is a said structure, the inventor infers that nesa coating of the present invention has good electroconductibility.
As stated, the principal element that constitutes the non-oxidized substance class nesa coating with above-mentioned brucite structure all is a light element, and its Clarke number is also big in addition, all is being superior to existing oxide-based nesa coating aspect economic aspect and the resource.In addition, the nesa coating of non-oxidized substance class has and possesses Mg (OH) 2Symmetric structure (brucite structure), so can think through under reducing atmosphere (for example hydrogen atmosphere) to the heating of this nesa coating, said brucite structure is decomposed, and is decomposed into hydrogenate, water vapour and the hydrocarbon of magnesium.If the hydrogenate of said magnesium is for example 1 * 10 -2Be heated to 400 ℃ under the vacuum about Pa, then can easily convert monomer magnesium to.That is, can easily obtain monomer magnesium by the nesa coating of said non-oxidized substance class, the nesa coating of said non-oxidized substance class is also advantageous aspect resource.
< transmittance >
The transmittance of nesa coating of the present invention in the scope of wavelength 350～2500nm is usually more than 80%.Especially (in 380～780nm) the wavelength region may, transsmissivity better is more than 80% at visible light.Transmittance in this specification sheets is that the assay method of formulating in the transsmissivity TP (JIS R1635) according to the fine ceramics film records.
< the ratio resistance of nesa coating >
Nesa coating of the present invention low more better more than resistance is usually 5 * 10 -1Below the Ω cm.Said is recording than the middle four probe method of formulating of resistivity TP (JIS R 1637) through the fine ceramics film than resistance.
< crystal grain of nesa coating >
The crystal grain that constitutes nesa coating of the present invention can be observed with scanning electron microscope.The median size of observed crystal grain better is in the scope of 30～500nm, is more preferably in the scope of 30～350nm, further is more preferably in the scope of 100～200nm.If median size is in said scope, then the smoothness of nesa coating improves, and the diffuse-reflectance in the visible region is inhibited, and the transparency of nesa coating improves.Above-mentioned median size is the median size based on the twin shaft average diameter with observed each crystal grain of scanning electron microscope.
[method of manufacture of nesa coating]
The method of manufacture of nesa coating of the present invention does not have special qualification, for example can adopt PVD (physical vapor vapor deposition) method through following method manufacturing.
As above-mentioned PVD (physical vapor vapor deposition) method, the method that belongs to the sputter class of can giving an example and vacuum vapour deposition, ionic fluid vapour deposition method, MBE (molecular beam epitaxy) method etc. belong to the method for evaporation type.The method that belongs to the sputter class is compared with the method that belongs to the evaporation class, need not high vacuum, and can carry out the film forming of the materials with high melting point of carbon and so on easily, and is therefore preferred.
The method of manufacture (1) of nesa coating that employing belongs to the method for sputter class is characterised in that; Use magniferous target of bag and the target that comprises at least a kind of element (A) that is selected from carbon, silicon and boron; On substrate, form the film that comprises magnesium and this element (A), this film is remained in the moisture atmosphere.
The method of manufacture (2) that employing belongs to the nesa coating of the method for evaporating class is characterised in that; Use magniferous evaporation source of bag and the evaporation source that comprises at least a kind of element (A) that is selected from carbon, silicon and boron; On substrate, form the film that comprises magnesium and this element (A), this film is remained in the moisture atmosphere.
[method of manufacture of nesa coating (1)]
First method of manufacture of nesa coating of the present invention is characterised in that, uses magniferous target of bag and the target that comprises at least a kind of element (A) that is selected from carbon, silicon and boron, on substrate, forms the film that comprises magnesium and this element (A), and this film is remained in the moisture atmosphere.
That is, nesa coating of the present invention can obtain through following method: use magniferous target of bag and the target that comprises at least a kind of element (A) that is selected from carbon, silicon and boron, on substrate, form the film that comprises magnesium and this element (A), this film is remained in the moisture atmosphere.
< wrapping magniferous target >
In the magniferous target of said bag that uses in the film forming of nesa coating of the present invention, the purity of magnesium more than 2N5 (99.5 weight %), better is more than 3N (99.9 weight %) usually.
Only otherwise can cause detrimentally affect to the light transmission and the electroconductibility of the nesa coating that formed by this target, the magniferous target of said bag also can comprise other element.
In addition, as the magniferous target of bag, also can use sputter with commercially available article such as magnesium targets.
< target that comprises at least a kind of element (A) that is selected from carbon, silicon and boron >
In the target of the said containing element (A) that uses in the film forming of nesa coating of the present invention, the purity of element (A) more than 2N5 (99.5 weight %), better is more than 3N (99.9 weight %) usually.As the moity of said target, only otherwise can cause detrimentally affect, also can comprise other element to the light transmission and the electroconductibility of the nesa coating that forms by this target.
In addition, as the target of said containing element (A), also can use commercially available article such as sputtering target.
As the target of said containing element (A), consider the carbonaceous target of preferred package from the angle of electroconductibility.As the carbonaceous target of said bag, consider more preferably graphite from the angle of electroconductibility.
The magniferous target of said bag that uses in the method for manufacture of nesa coating of the present invention and the weight ratio of the target of said containing element (A) are according to the atomic ratio of magnesium in the nesa coating of manufacturing and element (A) and different; The weight ratio (wrapping the target of magniferous target/containing element (A)) of wrapping the target of magniferous target and containing element (A) is usually in 0.6～40 scope; Better be in 1～20 scope, be more preferably in 2～10 scope.If in above-mentioned scope, then can the composition of gained nesa coating be set in the preferable range, can be made into nesa coating with good visible light transmission and electroconductibility.
The magniferous target of said bag that uses in the method for manufacture of nesa coating of the present invention and the surface area ratio of the target of said containing element (A) are according to the atomic ratio of magnesium in the nesa coating of manufacturing and element (A) and different; Surface area ratio (wrapping the target of magniferous target/containing element (A)) in 1.47～48.7 scope, better is in 2.40～33.6 scope usually.If in above-mentioned scope, then can the composition of gained nesa coating be set in the preferable range, can be made into nesa coating with good visible light transmission and electroconductibility.
In addition, also can use target with magniferous target of said bag and said containing element (A) to be configured to zyklopisch and mosaic target.
< film forming >
In the method for manufacture of nesa coating of the present invention, use the target of magniferous target of bag and said containing element (A) on substrate, to form the film that comprises magnesium and this element (A).
As above-mentioned film, can give an example and use the different target more than 2 of composition film forming method on substrate simultaneously, and use alternately film forming method on substrate of the different target more than 2 of composition.When making nesa coating, owing to control the composition of nesa coating easily, the therefore preferred target while film forming cosputtering method on substrate more than 2 of using composition different that adopts.
(cosputtering method)
When adopting above-mentioned cosputtering method, sputter equipment does not have special qualification, can use SPC-350 commercially available devices such as (An Neihua (ァ ネ Le バ) corporate systems).
As the sputter gas that uses in the cosputtering method, there is not qualification especially, the rare gas elementes such as argon, neon, xenon of can giving an example.Consider from the angle of sputtering rate and price, preferably use argon.
In addition; Sputtering power is generally 40～200W for the magniferous target of bag according to the atomic ratio of magnesium in the nesa coating of manufacturing and element (A) and different, is preferably 100～160W; Target for said containing element (A) is generally 100～500W, is preferably 300～400W.If sputtering power in said scope, then can be set in the magnesium of gained nesa coating and the atomic ratio of element (A) in the above-mentioned preferable range.
Consider that from the angle of the light transmission of target nesa coating and electroconductibility the thickness of the film that comprises magnesium and element (A) that gets through above-mentioned film forming in the scope of 0.1～5.0 μ m, better is in the scope of 1.0～3.5 μ m usually.Said thickness is 2 the average film thickness that records with AFM (AFM) and SEM (scanning electron microscope).
Film formation time is different according to comprising the thickness of the magnesium and the film of said element (A), is generally 2 minutes～12 hours, is preferably 3 minutes～5 hours.
(substrate)
The substrate that uses in first method of manufacture as nesa coating of the present invention does not have qualification especially, according to the purposes of nesa coating, can use glass substrate, polymeric substrate etc.For example, glass substrate is applicable to display panels, and polymeric substrate is applicable to transparent touch-sensitive panel.
In addition, best cleaning base plate before above-mentioned film forming.As scavenging solution, can use organic solvents such as ethanol for glass substrate, can use acid or alkaline solution etc. for polymeric substrate.In addition, as purging method, the ultrasonic cleaning etc. of can giving an example.
< moisture atmosphere >
In first method of manufacture of nesa coating of the present invention, remain in the moisture atmosphere, can obtain nesa coating through the film that comprises magnesium and said element (A) that will obtain as stated.Hold-time is set according to main aqueous atmosphere.
Said moisture atmosphere can be given an example in the atmosphere that for example comprises water vapour, water is medium.
(comprising in the atmosphere of water vapour)
The said atmospheric relative humidity that comprises water vapour in the scope of 30～100 weight %, better is in the scope of 40～100 weight % usually.When the film that will comprise magnesium and said element (A) remained in the atmosphere that comprises water vapour, relative humidity was high more, then can make an appointment with and obtain nesa coating soon, and is therefore preferred.But, in order to remain under the high humidity, need set high wet sump etc. separately, in industry, can come suitably to determine relative humidity according to the balance of desired production rate, cost etc.
When the film that will comprise magnesium and said element (A) remains in the atmosphere that comprises water vapour, usually through keeping to obtain to have the nesa coating of light transmission and electroconductibility more than 10 minutes.In general, the thickness of film that comprises magnesium and said element (A) is thin more, can set the hold-time short more, and relative humidity is high more, can set the hold-time short more.For example, when being formed in the atmosphere that comprises water vapour that the film that comprises magnesium and carbon (thickness 2.5 μ m) on the glass substrate remains in relative humidity 60 weight %, the hold-time is generally 10～30 minutes.
(in the water)
As said water, both can be tap water, also can be purified water, consider preferred tap water from the cost aspect, consider the preferred purified water that uses from the angle of the quality of gained film.
When the film that will comprise magnesium and said element (A) remained in the water, water temperature in 10～60 ℃ scope, better was in 20～30 ℃ scope usually.
When the film that will comprise magnesium and said element (A) remains in the water, more than 10 minutes, better be to keep the nesa coating that can obtain to have light transmission and electroconductibility 10～30 minutes through keeping usually.
[method of manufacture of nesa coating (2)]
Second method of manufacture of nesa coating of the present invention is characterised in that; Use magniferous evaporation source of bag and the evaporation source that comprises at least a kind of element (A) that is selected from carbon, silicon and boron; On substrate, form the film that comprises magnesium and this element (A), this film is remained in the moisture atmosphere.
Promptly; Nesa coating of the present invention can obtain through following method: use magniferous evaporation source of bag and the evaporation source that comprises at least a kind of element (A) that is selected from carbon, silicon and boron; On substrate, form the film that comprises magnesium and this element (A), this film is remained in the moisture atmosphere.
< wrapping magniferous evaporation source >
In the magniferous evaporation source of said bag that uses in the film forming of nesa coating of the present invention, the purity of magnesium more than 2N5 (99.5 weight %), better is more than 3N (99.9 weight %) usually.
Only otherwise can cause detrimentally affect to the light transmission and the electroconductibility of the nesa coating that formed by this evaporation source, the magniferous evaporation source of said bag also can comprise other element.
In addition, as the magniferous evaporation source of bag, also can use vapor deposition with commercially available article such as the piece of magnesium, powder, thin slice, particles.
< evaporation source that comprises at least a kind of element (A) that is selected from carbon, silicon and boron >
In the evaporation source of the said containing element (A) that uses in the film forming of nesa coating of the present invention, the purity of element (A) more than 2N5 (99.5 weight %), better is more than 3N (99.9 weight %) usually.As the moity of said evaporation source, only otherwise can cause detrimentally affect, also can comprise other element to the light transmission and the electroconductibility of the nesa coating that forms by this evaporation source.
In addition, as the evaporation source of containing element (A), also can use commercially available article such as piece that vapor deposition uses, powder, thin slice, particle.
As the evaporation source of said containing element (A), consider the carbonaceous evaporation source of preferred package from the angle of electroconductibility.As the carbonaceous evaporation source of said bag, consider more preferably graphite from the angle of electroconductibility.
< film forming >
In second method of manufacture of nesa coating of the present invention, use the evaporation source of magniferous evaporation source of bag and said containing element (A) on substrate, to form the film that comprises magnesium and this element (A).
As above-mentioned film, can give an example for example vacuum vapour deposition, ionic fluid vapour deposition method, MBE (molecular beam epitaxy) method etc.Wherein, owing to control the composition of nesa coating easily, therefore preferred MBE (molecular beam epitaxy) method of using.
(substrate)
The substrate that uses in second method of manufacture as nesa coating of the present invention, can use with above-mentioned first method of manufacture in the identical substrate of substrate put down in writing.
< moisture atmosphere >
In second method of manufacture of the present invention, remain in the moisture atmosphere identical, can obtain nesa coating with above-mentioned first method of manufacture through the film that comprises magnesium and said element (A) that will obtain as stated.
[purposes of nesa coating]
Nesa coating of the present invention has light transmission and electroconductibility, can be used as the resource exhaustion problem equivalent material of the ito thin film of seriousization just gradually.
For example, if on glass substrate, form nesa coating, then can be used as the surface electrode of solar cell or the drive electrode of liquid-crystal display.In addition, if on resin film substrate, form nesa coating, then can be used for the electrode of transparent touch-sensitive panel or EL (electroluminescent) flat lamp as transparent and electrically conductive film.
Embodiment
Based on embodiment the present invention is explained more specifically below, but the present invention is not limited to these embodiment.
[embodiment 1]
(preparing before the film forming)
The glass substrate (Pyrex (registered trademark) glass, thick 0.7mm, Dow Corning Corporation's system) that will in ethanol, carry out ultrasonic cleaning is installed on rotary substrate holder, and (revolution speed: 60rpm) (anode side) is disposed in the sputtering chamber with the sputter target surface abreast.
As sputtering target, magnesium (magnesium target, purity 3N (99.9 weight %), high-purity chemical research institute of Co., Ltd. ((strain) high-purity chemical research institute) system) and graphite (graphite, purity 3N (99.9 weight %), Ni Lake (ニ ラ コ) Co., Ltd.'s system) are disposed at cathode side.
Sputter equipment uses SPC-350 (An Neihua corporate system).
(film forming processing)
Reach 2.8 * 10 with vacuum pump with being decompressed to pressure in the sputtering chamber -3Pa.
Then, to the argon gas (Japanese elaboration Co., Ltd. (ジ ャ パ Application Off ァ ィ Application プ ロ ダ Network ッ (strain)) system purity 6N (99.9999 weight %) more than) of said indoor importing, total pressure is remained on 0.5Pa as sputter gas.The argon flow amount of this moment is set at 5.0sccm.
Through utilizing the plasma discharge of argon gas, be described below and carry out the preparatory sputter process of sputtering target.For the magnesium target, carry out 10 minutes preparatory sputter process with 100W, then carry out 10 minutes preparatory sputter process with 200W, carry out 10 minutes preparatory sputter process again with 100W.For graphite target, carry out 10 minutes preparatory sputter process with 100W, then carry out 10 minutes preparatory sputter process with 200W, carry out 5 minutes preparatory sputter process with 300W, carry out 5 minutes preparatory sputter process with 400W.
In advance after the sputter process; With the sputtering condition shown in the table 1; Through the cosputtering method magnesium and graphite are formed the film (MgC film) that comprises magnesium and carbon on said glass substrate, 2 the average film thickness that AFM that states after the usefulness of this film (AFM) and SEM (scanning electron microscope) record is 2.5 μ m.
Table 1 sputtering condition
Figure GPA00001102571900121
(film forming aftertreatment)
After above-mentioned film forming is handled, the sputter gas in the sputtering chamber is discharged, reach 5 * 10 until pressure with vacuum pump -3Pa.
Then, in sputtering chamber, take out the glass substrate that is formed with the MgC film, in the atmosphere that comprises water vapour of relative humidity 60 weight %, kept 15 minutes, obtain to be formed with the glass substrate of nesa coating by this.
(analysis of nesa coating)
(1) outward appearance of nesa coating
(1-1) outward appearance of nesa coating (range estimation)
When remaining in the atmosphere that comprises water vapour of relative humidity 60 weight % through the time change and be shown in Fig. 1.
Shown in Fig. 1 (a-1), under the state after the firm film forming, the color between color black in color (the metalluster)-grey of MgC film, light tight.But along with the increase of the hold-time in atmosphere ((a-1) [just after the film forming] → (a-2) [5 minutes hold-times] → (a-3) [10 minutes hold-times] → (a-4) [15 minutes hold-times]), the MgC film printing opacity that becomes has become nesa coating.
(1-2) outward appearance of nesa coating (transmittance)
Measure the transmittance of the nesa coating in wavelength 350～1000nm scope with ultraviolet-visible pectrophotometer.The result is shown in Fig. 2.The transmittance of the nesa coating in wavelength 350～1000nm scope is more than 80%.
Here, the transsmissivity (T of nesa coating 3) mensuration is described below.
Measure the transmittance (T of the nesa coating that comprises glass substrate with ultraviolet-visible pectrophotometer (Japanese beam split Co., Ltd. (Japanese beam split (strain)) system) 1[%]).Under the condition identical, only measure the transmittance (T of glass substrate with reference 2[%]), calculate the transsmissivity (T of nesa coating through following formula 3[%]).
T 3＝(T 1/T 2)×100[％]
Mensuration is carried out according to the assay method of formulating in the transsmissivity TP (JIS R 1635) of fine ceramics film.
(2) composition of nesa coating, structure
(2-1) mensuration of the X-ray diffraction of nesa coating
The X-ray diffraction result of nesa coating (thin-film material crystallinity Analysis of X ray diffraction device, Japanese Philip Co., Ltd. (Japanese Off ィ リ ッ プ ス (strain)) system) is shown in Fig. 3.Incident X-rays adopts CuK α line (40kV, 40mA), and input angle is made as 1 °.Come from Mg (OH) through observation 2The strong peak of (001) of structure, (101) and (110) face can know that nesa coating has and possesses Mg (OH) 2Symmetric structure (brucite structure).
(2-2) the x-ray photoelectron power spectrum of nesa coating
As shown in Figure 4; For nesa coating; Carry out etching and in each stage, carry out compositional analysis simultaneously from this film surface along depth direction with argon ion through XPS (x-ray photoelectron power spectrum, Ai Fakefei Co., Ltd. (ァ Le バ ッ Network Off ァ ィ (strain)) system), the magnesium in the nesa coating after average and the atomic ratio of carbon are magnesium/carbon=3.8 (atomic ratios) to the result with each stage.
(2-3) the Wavelength dispersion type ultimate analysis of nesa coating
A transparent conductive film WDX (wavelength dispersive element analysis, Shimadzu Corporation ((Ltd.) manufactured by Shimadzu) system) of the transparent conductive film was observed in magnesium, carbon and oxygen coexist.
Confirmed the existence of magnesium and carbon in above-mentioned (2-2), confirmed the existence of magnesium, carbon and oxygen in (2-3), and according to above-mentioned (2-1), nesa coating has had and possessed Mg (OH) 2Symmetric structure (brucite structure), infer thus, in nesa coating of the present invention, magnesium, carbon, oxygen and hydrogen coexistence.
In addition,, can know to comprise carbon in the nesa coating, and nesa coating is to possess Mg (OH) through Wavelength dispersion type ultimate analysis and above-mentioned x-ray photoelectron power spectrum 2Symmetric structure, (001) peak of nesa coating and Mg (OH) 2(001) peak compare to the low angle side shifting, promptly the interfloor distance of brucite structure enlarges, and infers thus, carbon atom (C) is fixed on the interlayer of brucite structure.
(2-4) atomic force microscope observation of nesa coating
Observe nesa coating with AFM (AFM, Keyemce company ((strain) キ one ェ Application ス) system).
Can know that by Fig. 5 the arithmetic average roughness Ra of the smoothness of expression nesa coating is 43nm.
(2-5) scanning electron microscope of nesa coating is observed
Observe nesa coating with SEM (scanning electron microscope, Hitachi Co., Ltd's ((strain) Hitachi splits and does institute) system).
Can know that by Fig. 6 the median size based on the twin shaft average diameter of the crystal grain of nesa coating is 150nm.
(2-6) mensuration of the ratio resistance of nesa coating
From the passing of four probe method (device name HiTESTER, Hioki Electric Corporation (HIOKI (strain)) the system) measured surface resistance of the transparent conductive film than the calculated resistance value.Its result is as shown in Figure 7, and according to extrapolated value, the ratio resistance value of nesa coating is 3 * 10 -1Ω cm.
Than resistance is recording than the middle four probe method of formulating of resistivity TP (JIS R 1637) through the fine ceramics film.
This than the value of resistance value and the existing ito thin film developed and ZnO film etc. about equally.
[embodiment 2]
Film forming is not that the glass substrate that is formed with the MgC film is remained in the atmosphere, but remains in (23 ℃ of temperature, time of immersion 30 minutes) in the zero(ppm) water after handling, and in addition likewise operates with embodiment 1, obtains being formed with the glass substrate of nesa coating.
[comparative example 1]
, film forming likewise carries out till handling with embodiment 1.
After film forming is handled, the sputter gas in the sputtering chamber is discharged, reach 5.0 * 10 until pressure with vacuum pump -3Pa.
Then, finish exhaust, in the sputtering chamber of sealed state, import drying nitrogen (Japanese oxygen Co., Ltd. (japanic acid plain (strain)) system is more than the purity 5N5 (99.9995 weight %)), total pressure is remained on 40kPa.
Then, the glass substrate that under dry nitrogen atmosphere, will be formed with the MgC film continues to observe indoor placement 48 hours.But above-mentioned MgC film is (metalluster) look～grey darkly, does not become transparent.
[comparative example 2]
After film forming is handled, not, but import dry oxygen (Japanese elaboration Co., Ltd. system) (more than the purity 6N5 (99.99995 weight %)), in addition likewise operate with comparative example 1 to indoor importing nitrogen.
Consequently, above-mentioned MgC film is (metalluster) look～grey darkly, does not become transparent.
[comparative example 3]
After film forming is handled, not, but import dry air (Japanese elaboration Co., Ltd. system), in addition likewise operate with comparative example 1 to indoor importing nitrogen.
Consequently, above-mentioned MgC film is (metalluster) look～grey darkly, does not become transparent.
[embodiment 3～5]
After carrying out the processing of above-mentioned comparative example 1～3, with the same condition of embodiment 1 under will be formed with the MgC film glass substrate remain in the atmosphere, obtain being formed with the glass substrate of nesa coating.
In the foregoing description 1,3～5, when remaining in the MgC film in the atmosphere that comprises water vapour, in embodiment 2, when remaining in the MgC film in the zero(ppm) water, the MgC film printing opacity that becomes has become nesa coating.In addition, can't obtain nesa coating with the atmosphere of comparative example, hence one can see that, when making nesa coating of the present invention, usefully the MgC film remained in the moisture atmosphere.
The possibility of utilizing on the industry
The transparency of nesa coating of the present invention and excellent conductivity, and do not use rare metal to be raw material, therefore can be used as the ITO equivalent material.

Claims (11)

1. a nesa coating is characterized in that, comprises magnesium, and carbon is selected from least a kind of elements A of silicon and boron, oxygen, hydrogen; The crystalline structure of said nesa coating has the brucite structure.
2. a nesa coating is characterized in that, comprises magnesium, carbon, oxygen, hydrogen; The crystalline structure of said nesa coating has the brucite structure.
3. nesa coating as claimed in claim 2 is characterized in that the atomic ratio of magnesium and carbon counts 0.3～20 with magnesium/carbon.
4. nesa coating; It is characterized in that; Obtain through following method: use the magniferous target of bag, wrap carbonaceous target, comprise the target of at least a kind of elements A that is selected from silicon and boron, on substrate, form the film that comprises magnesium, carbon and this elements A, this film is remained in the moisture atmosphere.
5. a nesa coating is characterized in that, obtains through following method: use magniferous target of bag and the carbonaceous target of bag, on substrate, form the film that comprises magnesium and carbon, this film is remained in the moisture atmosphere.
6. like claim 4 or 5 described nesa coatings, it is characterized in that said moisture atmosphere is atmosphere or the water that comprises water vapour.
7. like claim 4 or 5 described nesa coatings, it is characterized in that said film forming is carried out through the cosputtering method.
8. the method for manufacture of a nesa coating is characterized in that, uses the magniferous target of bag, wraps carbonaceous target, comprises the target of at least a kind of elements A that is selected from silicon and boron, on substrate, forms the film that comprises magnesium, carbon and this elements A, and this film is remained in the moisture atmosphere.
9. the method for manufacture of a nesa coating is characterized in that, uses magniferous target of bag and the carbonaceous target of bag, on substrate, forms the film that comprises magnesium and carbon, and this film is remained in the moisture atmosphere.
10. nesa coating; It is characterized in that; Obtain through following method: use the magniferous evaporation source of bag, wrap carbonaceous evaporation source, comprise the evaporation source of at least a kind of elements A that is selected from silicon and boron; On substrate, form the film that comprises magnesium, carbon and this elements A, this film is remained in the moisture atmosphere.
11. the method for manufacture of a nesa coating; It is characterized in that; Use the magniferous evaporation source of bag, wrap carbonaceous evaporation source, comprise the evaporation source of at least a kind of elements A that is selected from silicon and boron, on substrate, form the film that comprises magnesium, carbon and this elements A, this film is remained in the moisture atmosphere.
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